CN110614381B - Preparation method of silver-based graphene electrical contact material and electrical contact material thereof - Google Patents

Preparation method of silver-based graphene electrical contact material and electrical contact material thereof Download PDF

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CN110614381B
CN110614381B CN201910722410.XA CN201910722410A CN110614381B CN 110614381 B CN110614381 B CN 110614381B CN 201910722410 A CN201910722410 A CN 201910722410A CN 110614381 B CN110614381 B CN 110614381B
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nickel
copper
graphene
composite powder
vacuum
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CN110614381A (en
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黄光临
陈静
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Wenzhou Juxing Technology Co ltd
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Wenzhou Juxing Electric Contact Technology Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D19/00—Casting in, on, or around objects which form part of the product
    • B22D19/0072—Casting in, on, or around objects which form part of the product for making objects with integrated channels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/1017—Multiple heating or additional steps
    • B22F3/1021—Removal of binder or filler
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/11—Making porous workpieces or articles
    • B22F3/114—Making porous workpieces or articles the porous products being formed by impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24—After-treatment of workpieces or articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
    • B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H1/00—Contacts
    • H01H1/02—Contacts characterised by the material thereof
    • H01H1/021—Composite material
    • H01H1/023—Composite material having a noble metal as the basic material
    • H01H1/0233—Composite material having a noble metal as the basic material and containing carbides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H11/00—Apparatus or processes specially adapted for the manufacture of electric switches
    • H01H11/04—Apparatus or processes specially adapted for the manufacture of electric switches of switch contacts
    • H01H11/048—Apparatus or processes specially adapted for the manufacture of electric switches of switch contacts by powder-metallurgical processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24—After-treatment of workpieces or articles
    • B22F2003/248—Thermal after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • B22F2009/245—Reduction reaction in an Ionic Liquid [IL]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a preparation method of a silver-based graphene electrical contact material and the electrical contact material prepared by the same, wherein the preparation method comprises the following steps: firstly, preparing nickel/graphene composite powder; secondly, mixing the nickel/graphene composite powder prepared in the first step with copper powder to prepare copper/nickel/graphene composite powder; thirdly, preparing the copper/nickel/graphene composite powder prepared in the second step into a copper/nickel/graphene composite foam; and fourthly, infiltrating the copper/nickel/graphene composite foam body prepared in the third step with a silver infiltration sheet to obtain the silver/copper/nickel/graphene composite electric contact material. The silver-based graphene electrical contact material prepared by the invention has excellent mechanical properties and electrical properties.

Description

Preparation method of silver-based graphene electrical contact material and electrical contact material thereof
Technical Field
The invention relates to the technical field of materials, in particular to a preparation method of a silver-based graphene electric contact material and the electric contact material prepared by the same.
Background
The electrical contact, also called contact, contact or contact, is a contact part in electrical switches, instruments and meters, and is responsible for the tasks of switching on, carrying and breaking current, so its performance directly affects the reliability of the operation of the switching electrical appliances and instruments and meters. The electrical contact process is a complex physical process, and usually requires electrical contact materials with characteristics of high electrical conductivity, low contact resistance, high thermal conductivity, high wear resistance, corrosion resistance, impact resistance and the like. The electric contact material has a history of nearly 100 years, pure silver, pure gold and pure platinum are used as the contact material at first, the alloys such as Ag-Cu, Au-Ag, Pt-Ir or Pd-Ag and the like are adopted in 40 s in the 20 th world, and the multi-element noble metal and various noble metal composite materials are developed in 60 s. Graphene is a new carbonaceous material (typically within 10 nm thick) with a two-dimensional cellular lattice structure closely packed with carbon atoms. In 2004, Geim et al successfully stripped a single layer of carbon atoms from graphite by using a micromechanical stripping method, and the two-dimensional ordered carbon alone is called graphene by scientists, and is paid much attention due to its unique crystal structure characteristics, such as excellent electric conductivity, thermal conductivity, high strength and the like. Although the research development of the graphene reinforced metal matrix composite material is slow, the excellent electrical conductivity, thermal conductivity and mechanical properties of the graphene bring a great revolution to the improvement of the properties of the metal matrix composite material. The combination of the graphene and the traditional reinforcement is also the key for the significant breakthrough of the graphene, and the defects of the traditional material are made up by using certain properties of the graphene, so that the traditional material is optimized and improved.
The patent document with publication number CN104538214A discloses the following technical solutions: the CuTeWCSnO2/GRN comprises the following materials in percentage by mass: the foam copper alloy comprises the following components: WC: 1. SnO 2: 1. the balance of CuTe, wherein the Cu content in the CuTe alloy is 99.5 percent, and the balance of Te. The thickness of the graphene is within 10 nanometers, and the graphite covers 70-90% of the surface of the foam copper. The preparation process comprises the following steps: mixing the CuTe powder, the WC powder, the SnO2 powder and the pore-forming agent uniformly, pressing, sintering and forming pores, wherein the porosity is 50-90%, and preparing the copper foam block, wherein the organic pore-forming agent in the copper foam must be removed completely in the sintering process. The block is subjected to chemical vapor deposition of graphene in a tubular resistance furnace, a carbon source is methane, and the thickness of the graphene layer subjected to vapor deposition is controlled within a range of 10 nanometers. The prepared copper foam with the graphene on the pore wall is repeatedly rolled and pressed to prepare the copper alloy contact material of the compact body with the relative density of more than 99%. The copper-based contact prepared by the composition has the density of 8.62g/cm3, the resistivity of 2.28 mu omega cm and the hardness of HV 112.
The patent document with publication number CN102385938B discloses the following technical solutions: 1. preparing a 2% silver nitrate solution (solution A); 2. adding 0.4g of graphene with the average diameter of 50nm into a beaker with 20mLA solution, and uniformly dispersing by ultrasonic; 3. dropwise adding 1mL of 2% hydrazine hydrate solution into the solution, and magnetically stirring for 30 min; 4. centrifuging and washing with water for 3 times, and oven drying; 5. weighing 0.008g of the dried solid powder, and ball-milling and mixing the solid powder with 20g of silver powder for 2 hours; 6. vacuum melting is carried out by a vacuum melting method. And obtaining the graphene composite electric contact material.
The patent document with publication number CN108531764A discloses the following technical solutions: i) the material components of the silver/tungsten carbide/graphene/nickel electric contact material are mainly metallic silver, tungsten carbide, graphene and metallic nickel, wherein the content of tungsten carbide is 12 wt%, the content of graphene is 0.1 wt%, the content of nickel is 0.5 wt%, and the balance is silver. II) preparing silver/tungsten carbide/graphene/nickel electric contact materials, namely, the basic step 1) preparing 0.1mol/L silver nitrate solution, 0.1mol/L nickel nitrate solution and 0.1mol/L ascorbic acid solution. 2) According to the composition of the material components, a certain amount of ascorbic acid solution is mixed with graphene oxide solution with the mass concentration of 2%, and the mixture is uniformly stirred. 3) Mixing the mixed solution obtained in the step 1) and the mixed solution obtained in the step 2) with mechanical stirring or magneton stirring. And reducing the silver nitrate and the nickel nitrate by ascorbic acid, growing and depositing on the surface of the graphene oxide to generate a silver/graphene oxide/nickel suspension, settling, centrifugally washing and drying the silver/graphene oxide/nickel suspension to obtain the silver/graphene oxide/nickel composite powder. 4) The method comprises the following steps of (1) using a planetary ball mill, wherein the grinding balls are agate balls, the grinding pot is an agate pot, the liquid-phase medium is alcohol, and the ball-material ratio is 5: 1, mixing the obtained silver/graphene oxide/nickel composite powder with quantitative tungsten carbide powder for 8 hours to obtain the silver/tungsten carbide/graphene oxide/nickel composite powder. 5) And (2) heating and reducing the silver/tungsten carbide/graphene oxide/nickel composite powder for 2 hours at 400 ℃ in a hydrogen atmosphere to obtain the silver/tungsten carbide/graphene/nickel composite powder, wherein the tungsten carbide content is 12 wt%, the graphene content is 0.1 wt%, the nickel content is 0.5 wt%, and the balance is silver. 6) And pressing and molding the silver/tungsten carbide/graphene/nickel composite powder by using a compression molding technology to obtain a silver/tungsten carbide/graphene/nickel blank, placing the blank in a sintering furnace, and sintering at 870 ℃ for 13 hours in a hydrogen atmosphere to obtain the highly compact silver/tungsten carbide/graphene/nickel composite material.
In the prior art, the defects of poor combination and dispersibility and poor mechanical property and electrical property of the prepared electric contact material exist.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a preparation method of a silver-based graphene electrical contact material with excellent mechanical properties and electrical properties and the electrical contact material prepared by the preparation method.
In order to achieve the above object of the present invention, the technical solution of the present invention is specifically as follows:
a preparation method of a silver-based graphene electrical contact material comprises the following steps:
firstly, preparing nickel/graphene composite powder;
secondly, mixing the nickel/graphene composite powder prepared in the first step with copper powder to prepare copper/nickel/graphene composite powder;
thirdly, preparing the copper/nickel/graphene composite powder prepared in the second step into a copper/nickel/graphene composite foam;
and fourthly, infiltrating the copper/nickel/graphene composite foam body prepared in the third step with a silver infiltration sheet to obtain the silver/copper/nickel/graphene composite electric contact material.
The technical scheme of the invention is further provided with: the first step comprises the following steps: preparing 0.1mol/L nickel nitrate solution and 0.2mol/L glucose solution; mixing a glucose solution and a graphene oxide solution with the concentration of 0.5% according to the mass ratio of 100:1, carrying out ion stirring to obtain a mixed solution, adding a nickel nitrate solution into the mixed solution according to the volume ratio of 4:5, and continuing to carry out ion stirring; carrying out reduction reaction on nickel nitrate and glucose to generate nickel particles, adsorbing graphene oxide by nickel powder to obtain a nickel/graphene oxide suspension, centrifugally washing the silver/graphene oxide suspension, and freeze-drying to obtain nickel/graphene oxide composite powder; and heating and reducing the nickel/graphene oxide composite powder for 3-4 hours at 580-620 ℃ in a hydrogen atmosphere to obtain the nickel/graphene oxide composite powder.
The technical scheme of the invention is further provided with: the second step comprises the following steps: copper powder with the particle size of less than 10 micrometers and the nickel/graphene composite powder are mixed according to the mass ratio of 10: 1, uniformly mixing to obtain primary mixed copper/nickel/graphene composite powder, adding the primary mixed copper/nickel/graphene composite powder into a ball mill, and carrying out ball milling for 5-6 hours at a rotation speed of 250r/min under the protection of argon gas to obtain the copper/nickel/graphene composite powder.
The technical scheme of the invention is further provided with: the third step comprises: adding copper/nickel/graphene composite powder into a starch aqueous solution, and uniformly stirring to prepare paste; then putting the polyurethane sponge into pasty/graphene composite powder slurry for repeated impregnation until the pores of the polyurethane sponge are filled; vacuum drying is carried out to remove the moisture in the polyurethane sponge filled with the copper/nickel/graphene composite powder slurry; putting the polyurethane sponge after vacuum drying into a degreasing furnace for degreasing under the protection of protective gas; placing the degreased copper/nickel/graphene foam intermediate in a high-vacuum high-temperature sintering furnace, and heating to 800-850 ℃ at a certain heating rate for vacuum sintering; and (3) placing the copper/nickel/graphene foam intermediate after vacuum sintering and cooling in a vacuum annealing furnace for stress relief annealing treatment.
The technical scheme of the invention is further provided with: the third step comprises: heating starch with distilled water until the starch is dissolved to prepare a starch water solution with the mass percent of 5-8%; then adding 3-5 parts by mass of copper/nickel/graphene composite powder into 1 part by mass of the cooled starch aqueous solution, and uniformly stirring to prepare paste; then, the aperture is 0.56-0.72 mm, and the density is 0.025-0.035 g/cm 3 The polyurethane sponge is put into pasty/graphene composite powder slurry to be repeatedly soaked until the pores of the polyurethane sponge are filled with the slurry; and (3) vacuum drying to remove water in the polyurethane sponge filled with the copper/nickel/graphene composite powder slurry, wherein the vacuum degree is kept at 1-3 Pa, the drying temperature is 50-80 ℃, and the drying time is 4-8 hours.
The technical scheme of the invention is further provided with: the third step comprises: putting the polyurethane sponge after vacuum drying into a degreasing furnace for degreasing treatment under the protection of argon, wherein the condition control process comprises the following steps: introducing argon for at least 0.5 hour before heating to remove air in the furnace, raising the temperature from room to 250-300 ℃ at the speed of 1-3 ℃/min, preserving the temperature for 0.5-1 hour, and introducing argon at the speed of 0.5L/min; raising the temperature to 400-500 ℃ at the speed of 0.5-1 ℃/min, preserving the temperature for 2-2.5 hours, and introducing argon at the speed of 1L/min; and then turning off the power supply, cooling the degreased intermediate along with the furnace, introducing argon at the speed of 1L/min, and turning off the argon until the intermediate is cooled to room temperature to obtain the degreased copper/nickel/graphene foam intermediate.
The technical scheme of the invention is further provided with: the third step comprises: placing the degreased copper/nickel/graphene foam intermediate in a high-vacuum high-temperature sintering furnace, heating to 800-850 ℃ at a certain heating rate, and performing vacuum sintering, wherein the vacuum degree of the sintering furnace at least reaches 1 x 10 before heating -3 Pa, raising the temperature from room temperature to 380-420 ℃ at the speed of 10-15 ℃/min, and keeping the temperature for 0.5-1 hour, wherein the vacuum degree is 1 multiplied by 10 -4 Pa; raising the temperature to 600-650 ℃ at the speed of 8-10 ℃/min, preserving the heat for 0.5-1 hour, and keeping the vacuum degree at 1 multiplied by 10 -4 Pa～1×10 -3 Pa; raising the temperature to 800-850 ℃ at a speed of 6-8 ℃/min, preserving the heat for 2-2.5 hours, wherein the vacuum degree is 1 multiplied by 10 -4 Pa～1×10 -3 Pa; after sintering, the vacuum degree is 1X 10 -4 Pa～1×10 -3 Pa; cooling to 600-650 ℃ at the speed of 12-15 ℃/min, and preserving heat for 1-1.5 hours; cooling to 380-420 ℃ at the speed of 15-20 ℃/min, preserving heat for 1-1.5 hours, and then cooling along with the furnace; and obtaining the copper/nickel/graphene foam intermediate after vacuum sintering.
The technical scheme of the invention is further provided with: the third step comprises the following steps: placing the copper/nickel/graphene foam intermediate after vacuum sintering and cooling in a vacuum annealing furnace, heating to 350-400 ℃ at a certain heating rate, and performing stress relief annealing treatment, wherein the vacuum degree in the annealing furnace at least reaches 1 x 10 before heating -3 Pa, raising the temperature from room temperature to 350-400 ℃ at the speed of 12-15 ℃/min, and keeping the temperature for 4-4.5 hours with the vacuum degree of 1 multiplied by 10 -4 Pa～1×10 -3 Pa; cooling to 300-330 ℃ at a rate of 5-8 ℃/min, and keeping the temperature for 3-3.5 hours with a vacuum degree of 1 × 10 -4 Pa～1×10 -3 Pa; cooling to 150-200 ℃ at the speed of 10-12 ℃/min, preserving the heat for 1.5-2 hours, and keeping the vacuum degree at 1 multiplied by 10 -4 Pa～1×10 -3 Pa; cooling to room temperature at a rate of 20-23 deg.C/min with a vacuum degree of 1 × 10 -4 Pa; copper/nickel/graphene foam was prepared.
The technical scheme of the invention is further provided with: the fourth step comprises: putting the silver infiltration sheet and the copper/nickel/graphene foam into a mold, putting the mold into an infiltration furnace, and preserving heat for 7-8 hours at 900-930 ℃ in a vacuum stateWhen the temperature is raised to 980-1000 ℃ to the temperature after the heat preservation is finished, argon is filled into the furnace, and the air pressure is 0.5-1 multiplied by 10 6 Pa, and carrying out air pressure infiltration for 0.5-1 hour to finally obtain the silver/copper/nickel/graphene composite material.
The preparation method of the silver-based graphene electrical contact material and the electrical contact material prepared by the preparation method have the following advantages:
(1) the nickel/graphene composite powder is more uniformly distributed as a reinforcing substance so as to improve the mechanical property and the electrical property.
(2) The prepared copper/nickel/graphene foam body is infiltrated with a silver infiltration sheet, so that the interface bonding state is greatly improved, and the mechanical property and the electrical property are further improved.
(3) The copper/nickel/graphene foam is prepared by controlling sectional conditions, has uniform pore distribution and good mechanical property, and further improves the interface bonding state when being infiltrated with a silver infiltration sheet so as to further improve the mechanical property and the electrical property.
(4) The prepared silver/copper/nickel/graphene composite material has tensile strength of 372-397 MPa, elongation of 27-31% and resistivity of 2.01-2.06 mu omega cm, excellent mechanical property and electrical property and prolonged electrical life.
Drawings
FIG. 1 is a schematic microstructure of the copper/nickel/graphene foam produced in example 1;
fig. 2 is a schematic microstructure diagram of the silver/copper/nickel/graphene composite material prepared in example 1.
Detailed Description
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Example 1:
firstly, preparing nickel/graphene composite powder
1) Preparing 0.1mol/L nickel nitrate solution and 0.2mol/L glucose solution;
2) mixing a glucose solution with a graphene oxide solution with the concentration of 0.5% according to the mass ratio of 100:1, carrying out ionic stirring to obtain a mixed solution, adding a nickel nitrate solution into the mixed solution according to the volume ratio of 4:5, and continuing the ionic stirring. And (3) carrying out reduction reaction on the nickel nitrate and glucose to generate nickel particles, and adsorbing the graphene oxide by the nickel powder to obtain a nickel/graphene oxide turbid liquid. And (4) centrifugally washing the silver/graphene oxide suspension, and freeze-drying to obtain the nickel/graphene oxide composite powder.
3) And heating and reducing the nickel/graphene oxide composite powder for 3 hours at 600 ℃ in a hydrogen atmosphere to obtain the nickel/graphene oxide composite powder.
Secondly, preparing copper/nickel/graphene composite powder
Copper powder with the particle size of less than 10 microns and nickel/graphene composite powder are mixed according to the mass ratio of 10: 1, uniformly mixing to obtain primary mixed copper/nickel/graphene composite powder, adding the primary mixed copper/nickel/graphene composite powder into a ball mill, and carrying out ball milling for 5 hours at the rotating speed of 250r/min under the protection of argon gas to obtain the copper/nickel/graphene composite powder.
Thirdly, preparing the copper/nickel/graphene composite foam
1) Firstly, heating starch with distilled water until the starch is dissolved to prepare a starch water solution with the mass percent of 5%; then adding 3 parts by mass of copper/nickel/graphene composite powder into 1 part by mass of the cooled starch aqueous solution, and uniformly stirring to prepare paste; then the aperture is 0.70mm, and the density is 0.030g/cm 3 The polyurethane sponge is put into pasty/graphene composite powder slurry to be repeatedly soaked until the pores of the polyurethane sponge are filled with the slurry;
2) vacuum drying to remove water in the polyurethane sponge filled with the copper/nickel/graphene composite powder slurry, wherein the vacuum degree is kept at 1Pa, the drying temperature is 60 ℃, and the drying time is 4 hours;
3) putting the polyurethane sponge after vacuum drying into a degreasing furnace for degreasing treatment under the protection of argon, wherein the condition control process comprises the following steps: introducing argon for at least 0.5 hour before heating to remove air in the furnace, raising the temperature from room to 300 ℃ at the speed of 1 ℃/min, and keeping the temperature for 0.5 hour, wherein the argon introduction speed is 0.5L/min; raising the temperature to 400 ℃ at the speed of 0.5 ℃/min, preserving the heat for 2 hours, and introducing argon at the speed of 1L/min; then, turning off a power supply, cooling the degreased intermediate along with the furnace, introducing argon at a rate of 1L/min, and turning off the argon until the intermediate is cooled to room temperature to obtain a degreased copper/nickel/graphene foam intermediate;
4) placing the degreased copper/nickel/graphene foam intermediate in a high-vacuum high-temperature sintering furnace, heating to 800 ℃ at a certain heating rate, and performing vacuum sintering, wherein the vacuum degree of the sintering furnace at least reaches 1 x 10 before heating -3 Pa, from room temperature to 400 deg.C at a rate of 15 deg.C/min, maintaining for 0.5 hr at a vacuum of 1 × 10 -4 Pa; raising the temperature to 600 ℃ at the speed of 10 ℃/min, and keeping the temperature for 0.5 hour with the vacuum degree of 1 multiplied by 10 -4 Pa～1×10 -3 Pa; raising the temperature to 800 ℃ at the speed of 6 ℃/min, and keeping the temperature for 2 hours with the vacuum degree of 1 multiplied by 10 -3 Pa; after sintering, the vacuum degree is 1X 10 -4 Pa～1×10 -3 Pa; cooling to 600 ℃ at the speed of 15 ℃/min, and preserving heat for 1 hour; cooling to 400 ℃ at the speed of 15 ℃/min, preserving heat for 1 hour, and then cooling along with the furnace; obtaining a copper/nickel/graphene foam intermediate after vacuum sintering;
5) placing the copper/nickel/graphene foam intermediate after vacuum sintering and cooling in a vacuum annealing furnace, heating to 350 ℃ at a certain heating rate, and performing stress relief annealing treatment, wherein the vacuum degree in the annealing furnace at least reaches 1 x 10 before heating -3 Pa, from room temperature to 350 deg.C at a rate of 15 deg.C/min, maintaining for 4 hr at a vacuum of 1 × 10 -4 Pa～1×10 -3 Pa; cooling to 300 deg.C at a rate of 5 deg.C/min, maintaining for 3 hr at a vacuum degree of 1 × 10 -4 Pa～1×10 -3 Pa; cooling to 200 ℃ at the speed of 10-12 ℃/min, and keeping the temperature for 2 hours, wherein the vacuum degree is 1 multiplied by 10 -4 Pa; cooling to room temperature at a rate of 20 deg.C/min under a vacuum of 1 × 10 -4 Pa. And finally, carrying out conventional post-treatment to obtain the copper/nickel/graphene foam.
Fourth, preparing silver/copper/nickel/graphene composite material by infiltration
Putting the silver infiltration sheet and the copper/nickel/graphene foam into a mould, putting the mould into an infiltration furnace, preserving heat for 7 hours at 930 ℃ in a vacuum state, and preserving heat after finishing preserving heatHeating to 1000 deg.C, and introducing argon gas into the furnace at a pressure of 0.5 × 10 6 Pa, and carrying out a gas pressure infiltration process for 0.5 hour to finally obtain the silver/copper/nickel/graphene composite material.
Example 2
Firstly, preparing nickel/graphene composite powder
1) Preparing 0.1mol/L nickel nitrate solution and 0.2mol/L glucose solution;
2) mixing a glucose solution with a graphene oxide solution with the concentration of 0.5% according to the mass ratio of 100:1, carrying out ionic stirring to obtain a mixed solution, adding a nickel nitrate solution into the mixed solution according to the volume ratio of 4:5, and continuing the ionic stirring. And (3) carrying out reduction reaction on the nickel nitrate and glucose to generate nickel particles, and adsorbing the graphene oxide by the nickel powder to obtain a nickel/graphene oxide turbid liquid. And (4) centrifugally washing the silver/graphene oxide suspension, and freeze-drying to obtain the nickel/graphene oxide composite powder.
3) And heating and reducing the nickel/graphene oxide composite powder for 3.5 hours at 580 ℃ in a hydrogen atmosphere to obtain the nickel/graphene oxide composite powder.
Secondly, preparing copper/nickel/graphene composite powder
Copper powder with the particle size of less than 10 microns and nickel/graphene composite powder are mixed according to the mass ratio of 10: 1, uniformly mixing to obtain primary mixed copper/nickel/graphene composite powder, adding the primary mixed copper/nickel/graphene composite powder into a ball mill, and carrying out ball milling for 5 hours at the rotating speed of 250r/min under the protection of argon gas to obtain the copper/nickel/graphene composite powder.
Thirdly, preparing the copper/nickel/graphene composite foam
1) Heating starch with distilled water until the starch is dissolved to prepare a starch water solution with the mass percent of 5-8%; then adding 5 parts by mass of copper/nickel/graphene composite powder into 1 part by mass of the cooled starch aqueous solution, and uniformly stirring to prepare a paste; then the aperture is 0.56mm, and the density is 0.035g/cm 3 The polyurethane sponge is put into pasty/graphene composite powder slurry to be repeatedly soaked until the pores of the polyurethane sponge are filled with the slurry;
2) vacuum drying to remove water in the polyurethane sponge filled with the copper/nickel/graphene composite powder slurry, wherein the vacuum degree is kept at 3Pa, the drying temperature is 80 ℃, and the drying time is 7 hours;
3) putting the polyurethane sponge after vacuum drying into a degreasing furnace for degreasing treatment under the protection of argon, wherein the condition control process comprises the following steps: introducing argon for at least 0.5 hour before heating to remove air in the furnace, heating from room temperature to 250 ℃ at the speed of 3 ℃/min, and keeping the temperature for 1 hour, wherein the argon introduction speed is 0.5L/min; heating to 500 deg.C at a rate of 1 deg.C/min, maintaining for 2.5 hr, and introducing argon at a rate of 1L/min; turning off a power supply, cooling the degreased intermediate along with the furnace, introducing argon at a speed of 1L/min, and turning off the argon until the intermediate is cooled to room temperature to obtain a degreased copper/nickel/graphene foam intermediate;
4) placing the degreased copper/nickel/graphene foam intermediate in a high-vacuum high-temperature sintering furnace, heating to 850 ℃ at a certain heating rate, and performing vacuum sintering, wherein the vacuum degree of the sintering furnace at least reaches 1 x 10 before heating -3 Pa, from room temperature to 420 ℃ at the speed of 10-15 ℃/min, and keeping the temperature for 1 hour, wherein the vacuum degree is 1 multiplied by 10 -4 Pa; heating to 650 deg.C at a rate of 10 deg.C/min, maintaining for 1 hr at a vacuum degree of 1 × 10 -4 Pa; raising the temperature to 850 ℃ at the speed of 6 ℃/min, and keeping the temperature for 2.5 hours with the vacuum degree of 1 multiplied by 10 -3 Pa; after sintering, the vacuum degree is 1X 10 -3 Pa; cooling to 650 ℃ at the speed of 15 ℃/min, and preserving heat for 1.5 hours; cooling to 420 ℃ at the speed of 20 ℃/min, preserving heat for 1.5 hours, and then cooling along with the furnace; obtaining a copper/nickel/graphene foam intermediate after vacuum sintering;
5) placing the copper/nickel/graphene foam intermediate after vacuum sintering and cooling in a vacuum annealing furnace, heating to 400 ℃ at a certain heating rate, and performing stress relief annealing treatment, wherein the vacuum degree in the annealing furnace at least reaches 1 x 10 before heating -3 Pa, raising the temperature from room temperature to 400 ℃ at the speed of 15 ℃/min, and keeping the temperature for 4.5 hours with the vacuum degree of 1 multiplied by 10 -3 Pa; cooling to 330 deg.C at a rate of 8 deg.C/min, and maintaining for 3.5 hr at a vacuum degree of 1 × 10 -3 Pa; cooling to 200 deg.C at a rate of 12 deg.C/min, maintaining for 2 hr at a vacuum degree of 1 × 10 -4 Pa; cooling to room temperature at a rate of 23 deg.C/min under a vacuum of 1 × 10 -4 Pa. Finally, conventional post-treatment is carried out to prepare the copper/nickel/graphiteAn olefinic foam.
Fourth, preparing silver/copper/nickel/graphene composite material by infiltration
Putting the silver infiltration sheet and the copper/nickel/graphene foam into a mould, putting the mould into an infiltration furnace, preserving heat at 930 ℃ for 8 hours in a vacuum state, heating to 1050 ℃ after heat preservation, filling argon into the furnace after reaching the temperature, wherein the air pressure is 0.5 multiplied by 10 6 Pa, and carrying out a gas pressure infiltration process for 0.5 hour to finally obtain the silver/copper/nickel/graphene composite material.
Example 3
Firstly, preparing nickel/graphene composite powder
1) Preparing 0.1mol/L nickel nitrate solution and 0.2mol/L glucose solution;
2) mixing a glucose solution and a graphene oxide solution with the concentration of 0.5% according to the mass ratio of 100:1, carrying out ion stirring to obtain a mixed solution, adding a nickel nitrate solution into the mixed solution according to the volume ratio of 4:5, and continuing to carry out ion stirring. And (3) carrying out reduction reaction on nickel nitrate and glucose to generate nickel particles, and adsorbing graphene oxide by nickel powder to obtain a nickel/graphene oxide suspension. And (4) centrifugally washing the silver/graphene oxide suspension, and freeze-drying to obtain the nickel/graphene oxide composite powder.
3) And heating and reducing the nickel/graphene oxide composite powder for 3 hours at 580 ℃ in a hydrogen atmosphere to obtain the nickel/graphene oxide composite powder.
Secondly, preparing copper/nickel/graphene composite powder
Copper powder with the particle size of less than 10 microns and nickel/graphene composite powder are mixed according to the mass ratio of 10: 1, uniformly mixing to obtain primary mixed copper/nickel/graphene composite powder, adding the primary mixed copper/nickel/graphene composite powder into a ball mill, and carrying out ball milling for 5 hours at the rotating speed of 250r/min under the protection of argon gas to obtain the copper/nickel/graphene composite powder.
Thirdly, preparing the copper/nickel/graphene composite foam
1) Firstly, heating starch with distilled water until the starch is dissolved to prepare a starch water solution with the mass percent of 5%; then adding 3 parts by mass of copper/nickel/graphene composite powder into 1 part by mass of the cooled starch aqueous solution, and uniformly stirring to prepare paste; then the aperture is 0.56mm, and the density is 0.025g/cm 3 The polyurethane sponge is put into pasty/graphene composite powder slurry to be repeatedly impregnated until the pores of the polyurethane sponge are filled with the slurry;
2) vacuum drying to remove water in the polyurethane sponge filled with the copper/nickel/graphene composite powder slurry, wherein the vacuum degree is kept at 1Pa, the drying temperature is 50 ℃, and the drying time is 4 hours;
3) putting the polyurethane sponge after vacuum drying into a degreasing furnace for degreasing treatment under the protection of argon, wherein the condition control process comprises the following steps: introducing argon for at least 0.5 hour before heating to remove air in the furnace, raising the temperature from the room to 250 ℃ at the speed of 1 ℃/min, and keeping the temperature for 0.5 hour, wherein the argon introduction speed is 0.5L/min; raising the temperature to 400 ℃ at the speed of 0.5 ℃/min, preserving the heat for 2 hours, and introducing argon at the speed of 1L/min; then, turning off a power supply, cooling the degreased intermediate along with the furnace, introducing argon at a rate of 1L/min, and turning off the argon until the intermediate is cooled to room temperature to obtain a degreased copper/nickel/graphene foam intermediate;
4) placing the degreased copper/nickel/graphene foam intermediate in a high-vacuum high-temperature sintering furnace, heating to 800 ℃ at a certain heating rate, and performing vacuum sintering, wherein the vacuum degree of the sintering furnace at least reaches 1 x 10 before heating -3 Pa, raising the temperature from room temperature to 380 ℃ at the speed of 10 ℃/min, and keeping the temperature for 0.5 hour, wherein the vacuum degree is 1 multiplied by 10 -4 Pa; heating to 600 deg.C at a rate of 8 deg.C/min, maintaining for 0.5 hr at a vacuum degree of 1 × 10 -4 Pa; raising the temperature to 800 ℃ at the speed of 6 ℃/min, and keeping the temperature for 2 hours with the vacuum degree of 1 multiplied by 10 -3 Pa; after sintering, the vacuum degree is 1X 10 -4 Pa; cooling to 600 ℃ at the speed of 12 ℃/min, and preserving heat for 1 hour; cooling to 380 deg.C at a rate of 15 deg.C/min, maintaining for 1 hr, and furnace cooling; obtaining a copper/nickel/graphene foam intermediate after vacuum sintering;
5) placing the copper/nickel/graphene foam intermediate after vacuum sintering and cooling in a vacuum annealing furnace, heating to 350 ℃ at a certain heating rate, and performing stress relief annealing treatment, wherein the vacuum degree in the annealing furnace at least reaches 1 x 10 before heating -3 Pa, raising the temperature from room temperature to 350 ℃ at the speed of 12 ℃/min, and keeping the temperature for 4 hours with the vacuum degree of 1 multiplied by 10 -4 Pa; cooling to 300 deg.C at a rate of 5 deg.C/minKeeping the temperature for 3 hours and the vacuum degree is 1 multiplied by 10 -4 Pa; cooling to 150 deg.C at a rate of 10 deg.C/min, maintaining for 1.5 hr at a vacuum degree of 1 × 10 -4 Pa; cooling to room temperature at a rate of 20 deg.C/min under a vacuum of 1 × 10 -4 Pa. And finally, carrying out conventional post-treatment to obtain the copper/nickel/graphene foam.
Fourth, preparing silver/copper/nickel/graphene composite material by infiltration
Putting a silver infiltration sheet and a copper/nickel/graphene foam body into a mould, putting the mould into an infiltration furnace, preserving heat for 7 hours at 900 ℃ in a vacuum state, heating to 980 ℃ after heat preservation, filling argon into the furnace after reaching the temperature, wherein the air pressure is 1 multiplied by 10 6 Pa, carrying out air pressure infiltration for 1 hour to finally obtain the silver/copper/nickel/graphene composite material.
Example 4
Firstly, preparing nickel/graphene composite powder
1) Preparing 0.1mol/L nickel nitrate solution and 0.2mol/L glucose solution;
2) mixing a glucose solution with a graphene oxide solution with the concentration of 0.5% according to the mass ratio of 100:1, carrying out ionic stirring to obtain a mixed solution, adding a nickel nitrate solution into the mixed solution according to the volume ratio of 4:5, and continuing the ionic stirring. And (3) carrying out reduction reaction on the nickel nitrate and glucose to generate nickel particles, and adsorbing the graphene oxide by the nickel powder to obtain a nickel/graphene oxide turbid liquid. And (3) centrifugally washing the silver/graphene oxide turbid liquid, and freeze-drying to obtain the nickel/graphene oxide composite powder.
3) And (3) heating and reducing the nickel/graphene oxide composite powder for 3.3 hours at 590 ℃ in a hydrogen atmosphere to obtain the nickel/graphene oxide composite powder.
Secondly, preparing copper/nickel/graphene composite powder
Copper powder with the particle size of less than 10 microns and nickel/graphene composite powder are mixed according to the mass ratio of 10: 1, uniformly mixing to obtain primary mixed copper/nickel/graphene composite powder, adding the primary mixed copper/nickel/graphene composite powder into a ball mill, and carrying out ball milling for 5.5 hours at the rotating speed of 250r/min under the protection of argon gas to obtain the copper/nickel/graphene composite powder.
Thirdly, preparing the copper/nickel/graphene composite foam
1) Firstly, starch is obtainedHeating the mixture by using distilled water until the mixture is dissolved to prepare a starch water solution with the mass percent of 7%; then adding 4 parts by mass of copper/nickel/graphene composite powder into 1 part by mass of the cooled starch aqueous solution, and uniformly stirring to prepare paste; then the aperture is 0.62mm, the density is 0.028g/cm 3 The polyurethane sponge is put into pasty/graphene composite powder slurry to be repeatedly soaked until the pores of the polyurethane sponge are filled with the slurry;
2) vacuum drying to remove water in the polyurethane sponge filled with the copper/nickel/graphene composite powder slurry, wherein the vacuum degree is kept at 1.5Pa, the drying temperature is 70 ℃, and the drying time is 7 hours;
3) putting the polyurethane sponge after vacuum drying into a degreasing furnace for degreasing treatment under the protection of argon, wherein the condition control process comprises the following steps: introducing argon for at least 0.5 hour before heating to remove air in the furnace, heating from room temperature to 260 ℃ at the speed of 1.5 ℃/min, keeping the temperature for 0.7 hour, and introducing argon at the speed of 0.5L/min; raising the temperature to 450 ℃ at the speed of 0.6 ℃/min, preserving the heat for 2.2 hours, and introducing argon at the speed of 1L/min; then, turning off a power supply, cooling the degreased intermediate along with the furnace, introducing argon at a rate of 1L/min, and turning off the argon until the intermediate is cooled to room temperature to obtain a degreased copper/nickel/graphene foam intermediate;
4) placing the degreased copper/nickel/graphene foam intermediate in a high-vacuum high-temperature sintering furnace, heating to 830 ℃ at a certain heating rate, and performing vacuum sintering, wherein the vacuum degree of the sintering furnace at least reaches 1 x 10 before heating -3 Pa, raising the temperature from room temperature to 390 ℃ at the speed of 12 ℃/min, and keeping the temperature for 0.6 hour with the vacuum degree of 1 multiplied by 10 -4 Pa; raising the temperature to 620 ℃ at the speed of 9 ℃/min, and keeping the temperature for 0.6 hour with the vacuum degree of 5 multiplied by 10 -4 Pa; heating to 830 deg.C at a rate of 8 deg.C/min, maintaining for 2.2 hr under a vacuum of 1 × 10 -3 Pa; after sintering, the vacuum degree is 5X 10 -4 Pa; cooling to 620 ℃ at the speed of 13 ℃/min, and preserving heat for 1.2 hours; cooling to 390 ℃ at the speed of 17 ℃/min, preserving heat for 1.2 hours, and then cooling along with the furnace; obtaining a copper/nickel/graphene foam intermediate after vacuum sintering;
5) placing the copper/nickel/graphene foam intermediate after vacuum sintering and cooling in a vacuum annealing furnaceHeating to 370 deg.C at a certain heating rate to perform stress relief annealing treatment, wherein the vacuum degree in the annealing furnace is at least 1 × 10 before heating -3 Pa, raising the temperature from room temperature to 370 ℃ at the speed of 13 ℃/min, and keeping the temperature for 4-4.5 hours with the vacuum degree of 1 multiplied by 10 -4 Pa～1×10 -3 Pa; cooling to 310 ℃ at the speed of 5-8 ℃/min, and preserving the heat for 3.2 hours with the vacuum degree of 5 multiplied by 10 -4 Pa; cooling to 170 deg.C at a rate of 11 deg.C/min, maintaining for 1.6 hr at a vacuum degree of 1 × 10 -4 Pa; cooling to room temperature at a rate of 21 deg.C/min and a vacuum of 1 × 10 -4 Pa. And finally, carrying out conventional post-treatment to obtain the copper/nickel/graphene foam.
Fourth, preparing silver/copper/nickel/graphene composite material by infiltration
Putting the silver infiltration sheet and the copper/nickel/graphene foam into a mold, putting the mold into an infiltration furnace, preserving heat for 7.5 hours at 920 ℃ in a vacuum state, raising the temperature to 990 ℃ after heat preservation, filling argon into the furnace after reaching the temperature, wherein the air pressure is 0.5 multiplied by 10 6 Pa, and carrying out a gas pressure infiltration process for 0.6 hour to finally obtain the silver/copper/nickel/graphene composite material.
Example 5
Firstly, preparing nickel/graphene composite powder
1) Preparing 0.1mol/L nickel nitrate solution and 0.2mol/L glucose solution;
2) mixing a glucose solution and a graphene oxide solution with the concentration of 0.5% according to the mass ratio of 100:1, carrying out ion stirring to obtain a mixed solution, adding a nickel nitrate solution into the mixed solution according to the volume ratio of 4:5, and continuing to carry out ion stirring. And (3) carrying out reduction reaction on nickel nitrate and glucose to generate nickel particles, and adsorbing graphene oxide by nickel powder to obtain a nickel/graphene oxide suspension. And (4) centrifugally washing the silver/graphene oxide suspension, and freeze-drying to obtain the nickel/graphene oxide composite powder.
3) And heating and reducing the nickel/graphene oxide composite powder for 3.6 hours at 610 ℃ in a hydrogen atmosphere to obtain the nickel/graphene oxide composite powder.
Secondly, preparing copper/nickel/graphene composite powder
Copper powder with the particle size of less than 10 microns and nickel/graphene composite powder are mixed according to the mass ratio of 10: 1, uniformly mixing to obtain primary mixed copper/nickel/graphene composite powder, adding the primary mixed copper/nickel/graphene composite powder into a ball mill, and carrying out ball milling for 5.7 hours at the rotating speed of 250r/min under the protection of argon gas to obtain the copper/nickel/graphene composite powder.
Thirdly, preparing the copper/nickel/graphene composite foam
1) Firstly, heating starch with distilled water until the starch is dissolved to prepare a 7% starch water solution by mass; then adding 4 parts by mass of copper/nickel/graphene composite powder into 1 part by mass of the cooled starch aqueous solution, and uniformly stirring to prepare paste; then the aperture is 0.65mm, the density is 0.033g/cm 3 The polyurethane sponge is put into pasty/graphene composite powder slurry to be repeatedly soaked until the pores of the polyurethane sponge are filled with the slurry;
2) vacuum drying to remove water in the polyurethane sponge filled with the copper/nickel/graphene composite powder slurry, wherein the vacuum degree is kept at 2Pa, the drying temperature is 70 ℃, and the drying time is 6 hours;
3) putting the polyurethane sponge after vacuum drying into a degreasing furnace for degreasing treatment under the protection of argon, wherein the condition control process comprises the following steps: introducing argon for at least 0.5 hour before heating to remove air in the furnace, raising the temperature from room to 280 ℃ at the speed of 2.5 ℃/min, and keeping the temperature for 0.8 hour, wherein the argon introduction speed is 0.5L/min; heating to 480 ℃ at the speed of 0.9 ℃/min, preserving the heat for 2.3 hours, and introducing argon at the speed of 1L/min; then, turning off a power supply, cooling the degreased intermediate along with the furnace, introducing argon at a rate of 1L/min, and turning off the argon until the intermediate is cooled to room temperature to obtain a degreased copper/nickel/graphene foam intermediate;
4) placing the degreased copper/nickel/graphene foam intermediate in a high-vacuum high-temperature sintering furnace, heating to 830 ℃ at a certain heating rate, and performing vacuum sintering, wherein the vacuum degree of the sintering furnace at least reaches 1 x 10 before heating -3 Pa, from room temperature to 410 deg.C at a rate of 13 deg.C/min, maintaining for 0.8 hr at a vacuum of 1 × 10 -4 Pa; raising the temperature to 630 ℃ at the speed of 9 ℃/min, and keeping the temperature for 0.5 hour with the vacuum degree of 1 multiplied by 10 -4 Pa; raising the temperature to 830 ℃ at the speed of 8 ℃/min, and preserving the heat for 2 hours with the vacuum degree of 1 multiplied by 10 -3 Pa; after sintering, the vacuum degree is 1X 10 -3 Pa；Cooling to 600 ℃ at the speed of 12 ℃/min, and preserving heat for 1.5 hours; cooling to 380 ℃ at the speed of 20 ℃/min, preserving heat for 1.5 hours, and then cooling along with the furnace; obtaining a copper/nickel/graphene foam intermediate after vacuum sintering;
5) placing the copper/nickel/graphene foam intermediate after vacuum sintering and cooling in a vacuum annealing furnace, heating to 380 ℃ at a certain heating rate for stress relief annealing treatment, wherein the vacuum degree in the annealing furnace at least reaches 1 x 10 before heating -3 Pa, from room temperature to 380 ℃ at a rate of 15 ℃/min, maintaining the temperature for 4.5 hours at a vacuum of 1X 10 -3 Pa; cooling to 300 deg.C at a rate of 8 deg.C/min, maintaining for 3 hr at a vacuum degree of 1 × 10 -3 Pa; cooling to 150 deg.C at a rate of 12 deg.C/min, maintaining for 1.5 hr with a vacuum degree of 1 × 10 -4 Pa; cooling to room temperature at a rate of 23 deg.C/min under a vacuum of 1 × 10 -4 Pa. And finally, carrying out conventional post-treatment to obtain the copper/nickel/graphene foam.
Fourth, preparing silver/copper/nickel/graphene composite material by infiltration
Putting the silver infiltration sheet and the copper/nickel/graphene foam into a mould, putting the mould into an infiltration furnace, preserving heat for 7.5 hours at 910 ℃ in a vacuum state, raising the temperature to 980 ℃ after the heat preservation is finished, filling argon into the furnace after the temperature is reached, and ensuring that the air pressure is 0.7 multiplied by 10 6 Pa, carrying out air pressure infiltration for 1 hour to finally obtain the silver/copper/nickel/graphene composite material.
Example 6
Firstly, preparing nickel/graphene composite powder
1) Preparing 0.1mol/L nickel nitrate solution and 0.2mol/L glucose solution;
2) mixing a glucose solution and a graphene oxide solution with the concentration of 0.5% according to the mass ratio of 100:1, carrying out ion stirring to obtain a mixed solution, adding a nickel nitrate solution into the mixed solution according to the volume ratio of 4:5, and continuing to carry out ion stirring. And (3) carrying out reduction reaction on the nickel nitrate and glucose to generate nickel particles, and adsorbing the graphene oxide by the nickel powder to obtain a nickel/graphene oxide turbid liquid. And (4) centrifugally washing the silver/graphene oxide suspension, and freeze-drying to obtain the nickel/graphene oxide composite powder.
3) And heating and reducing the nickel/graphene oxide composite powder for 3-4 hours at 580-620 ℃ in a hydrogen atmosphere to obtain the nickel/graphene oxide composite powder.
Secondly, preparing copper/nickel/graphene composite powder
Copper powder with the particle size of less than 10 microns and nickel/graphene composite powder are mixed according to the mass ratio of 10: 1, uniformly mixing to obtain primary mixed copper/nickel/graphene composite powder, adding the primary mixed copper/nickel/graphene composite powder into a ball mill, and carrying out ball milling for 5-6 hours at a rotation speed of 250r/min under the protection of argon gas to obtain the copper/nickel/graphene composite powder.
Thirdly, preparing the copper/nickel/graphene composite foam
1) Heating starch with distilled water until the starch is dissolved to prepare a starch water solution with the mass percent of 5-8%; then adding 3-5 parts by mass of copper/nickel/graphene composite powder into 1 part by mass of the cooled starch aqueous solution, and uniformly stirring to prepare paste; then the aperture is 0.70mm, the density is 0.033g/cm 3 The polyurethane sponge is put into pasty/graphene composite powder slurry to be repeatedly impregnated until the pores of the polyurethane sponge are filled with the slurry;
2) vacuum drying to remove water in the polyurethane sponge filled with the copper/nickel/graphene composite powder slurry, wherein the vacuum degree is kept at 2Pa, the drying temperature is 60 ℃, and the drying time is 6 hours;
3) putting the polyurethane sponge after vacuum drying into a degreasing furnace for degreasing treatment under the protection of argon, wherein the condition control process comprises the following steps: introducing argon for at least 0.5 hour before heating to remove air in the furnace, raising the temperature from the room to 260 ℃ at the speed of 2 ℃/min, and keeping the temperature for 1 hour, wherein the argon introduction speed is 0.5L/min; heating to 500 deg.C at a rate of 1 deg.C/min, maintaining for 2 hr, and introducing argon at a rate of 1L/min; turning off a power supply, cooling the degreased intermediate along with the furnace, introducing argon at a speed of 1L/min, and turning off the argon until the intermediate is cooled to room temperature to obtain a degreased copper/nickel/graphene foam intermediate;
4) placing the degreased copper/nickel/graphene foam intermediate in a high-vacuum high-temperature sintering furnace, heating to 850 ℃ at a certain heating rate, and performing vacuum sintering, wherein the vacuum degree of the sintering furnace at least reaches 1 x 10 before heating -3 Pa, rising from room temperature at a rate of 15 ℃/minKeeping the temperature at 420 ℃ for 0.5 hour with the vacuum degree of 1 multiplied by 10 -4 Pa; heating to 650 deg.C at a rate of 10 deg.C/min, maintaining for 0.5 hr at a vacuum degree of 1 × 10 -3 Pa; heating to 880 deg.C at 8 deg.C/min, maintaining the temperature for 2 hr at a vacuum degree of 1 × 10 -3 Pa; after sintering, the vacuum degree is 1X 10 -3 Pa; cooling to 600 ℃ at the speed of 12 ℃/min, and preserving heat for 1.5 hours; cooling to 380 deg.C at a rate of 20 deg.C/min, maintaining for 1.5 hr, and furnace cooling; obtaining a copper/nickel/graphene foam intermediate after vacuum sintering;
5) placing the copper/nickel/graphene foam intermediate after vacuum sintering and cooling in a vacuum annealing furnace, heating to 350 ℃ at a certain heating rate, and performing stress relief annealing treatment, wherein the vacuum degree in the annealing furnace at least reaches 1 x 10 before heating -3 Pa, from room temperature to 350 deg.C at a rate of 12 deg.C/min, maintaining for 4.5 hr at a vacuum degree of 1 × 10 -4 Pa; cooling to 300 deg.C at a rate of 8 deg.C/min, maintaining for 3.5 hr at a vacuum degree of 1 × 10 -4 Pa; cooling to 150 deg.C at a rate of 12 deg.C/min, maintaining for 2 hr at a vacuum degree of 1 × 10 -4 Pa; cooling to room temperature at a rate of 20 deg.C/min under a vacuum of 1 × 10 -4 Pa. And finally, carrying out conventional post-treatment to obtain the copper/nickel/graphene foam.
Fourth, preparing silver/copper/nickel/graphene composite material by infiltration
Putting the silver infiltration sheet and the copper/nickel/graphene foam into a mould, putting the mould into an infiltration furnace, preserving heat at 920 ℃ for 7 hours in a vacuum state, heating to 1000 ℃ after heat preservation, filling argon into the furnace after reaching the temperature, wherein the air pressure is 0.8 multiplied by 10 6 Pa, and carrying out a gas pressure infiltration process for 0.5 hour to finally obtain the silver/copper/nickel/graphene composite material.
Example 7
Firstly, preparing nickel/graphene composite powder
1) Preparing 0.1mol/L nickel nitrate solution and 0.2mol/L glucose solution;
2) mixing a glucose solution and a graphene oxide solution with the concentration of 0.5% according to the mass ratio of 100:1, carrying out ion stirring to obtain a mixed solution, adding a nickel nitrate solution into the mixed solution according to the volume ratio of 4:5, and continuing to carry out ion stirring. And (3) carrying out reduction reaction on the nickel nitrate and glucose to generate nickel particles, and adsorbing the graphene oxide by the nickel powder to obtain a nickel/graphene oxide turbid liquid. And (4) centrifugally washing the silver/graphene oxide suspension, and freeze-drying to obtain the nickel/graphene oxide composite powder.
3) And (3) heating and reducing the nickel/graphene oxide composite powder for 3.3 hours at 590 ℃ in a hydrogen atmosphere to obtain the nickel/graphene oxide composite powder.
Secondly, preparing copper/nickel/graphene composite powder
Copper powder with the particle size of less than 10 microns and nickel/graphene composite powder are mixed according to the mass ratio of 10: 1, uniformly mixing to obtain primary mixed copper/nickel/graphene composite powder, adding the primary mixed copper/nickel/graphene composite powder into a ball mill, and carrying out ball milling for 5.6 hours at the rotating speed of 250r/min under the protection of argon gas to obtain the copper/nickel/graphene composite powder.
Thirdly, preparing the copper/nickel/graphene composite foam
1) Firstly, heating starch with distilled water until the starch is dissolved to prepare a starch water solution with the mass percent of 5%; then adding 3 parts by mass of copper/nickel/graphene composite powder into 1 part by mass of the cooled starch aqueous solution, and uniformly stirring to prepare paste; then the aperture is 0.62mm, the density is 0.025g/cm 3 The polyurethane sponge is put into pasty/graphene composite powder slurry to be repeatedly soaked until the pores of the polyurethane sponge are filled with the slurry;
2) vacuum drying to remove water in the polyurethane sponge filled with the copper/nickel/graphene composite powder slurry, wherein the vacuum degree is kept at 3Pa, the drying temperature is 50 ℃, and the drying time is 4 hours;
3) putting the polyurethane sponge after vacuum drying into a degreasing furnace for degreasing treatment under the protection of argon, wherein the condition control process comprises the following steps: introducing argon for at least 0.5 hour before heating to remove air in the furnace, raising the temperature from the room to 250 ℃ at the speed of 1 ℃/min, and keeping the temperature for 1 hour, wherein the argon introduction speed is 0.5L/min; raising the temperature to 400 ℃ at the speed of 0.5 ℃/min, preserving the heat for 2.5 hours, and introducing argon at the speed of 1L/min; then, turning off a power supply, cooling the degreased intermediate along with the furnace, introducing argon at a rate of 1L/min, and turning off the argon until the intermediate is cooled to room temperature to obtain a degreased copper/nickel/graphene foam intermediate;
4) placing the degreased copper/nickel/graphene foam intermediate in a high-vacuum high-temperature sintering furnace, heating to 850 ℃ at a certain heating rate, and performing vacuum sintering, wherein the vacuum degree of the sintering furnace at least reaches 1 x 10 before heating -3 Pa, raising the temperature from room temperature to 380-420 ℃ at the speed of 10-15 ℃/min, and keeping the temperature for 0.5-1 hour, wherein the vacuum degree is 1 multiplied by 10 -4 Pa; raising the temperature to 600-650 ℃ at the speed of 8-10 ℃/min, preserving the heat for 0.5-1 hour, and keeping the vacuum degree at 1 multiplied by 10 -4 Pa～1×10 -3 Pa; raising the temperature to 850 ℃ at the speed of 8 ℃/min, and preserving the heat for 2 hours with the vacuum degree of 1 multiplied by 10 -3 Pa; after sintering, the vacuum degree is 1X 10 - 4 PaPa; cooling to 650 ℃ at the speed of 15 ℃/min, and preserving heat for 1 hour; cooling to 380 deg.C at a rate of 20 deg.C/min, maintaining for 1.5 hr, and furnace cooling; obtaining a copper/nickel/graphene foam intermediate after vacuum sintering;
5) placing the copper/nickel/graphene foam intermediate after vacuum sintering and cooling in a vacuum annealing furnace, heating to 380 ℃ at a certain heating rate for stress relief annealing treatment, wherein the vacuum degree in the annealing furnace at least reaches 1 x 10 before heating -4 Pa, raising the temperature from room temperature to 380 ℃ at the speed of 15 ℃/min, and keeping the temperature for 4 hours, wherein the vacuum degree is 1 multiplied by 10 -4 Pa; cooling to 300 deg.C at a rate of 8 deg.C/min, maintaining for 3.5 hr at a vacuum degree of 1 × 10 -4 Pa; cooling to 160 deg.C at a rate of 12 deg.C/min, maintaining for 2 hr at a vacuum degree of 1 × 10 -4 Pa; cooling to room temperature at a rate of 20 deg.C/min under a vacuum of 1 × 10 -4 Pa. And finally, carrying out conventional post-treatment to obtain the copper/nickel/graphene foam.
Fourth, preparing silver/copper/nickel/graphene composite material by infiltration
Putting the silver infiltration sheet and the copper/nickel/graphene foam into a mould, putting the mould into an infiltration furnace, preserving heat at 930 ℃ for 7 hours in a vacuum state, heating to 990 ℃ after heat preservation, filling argon into the furnace after the temperature is reached, wherein the air pressure is 0.5 multiplied by 10 6 Pa, and carrying out a gas pressure infiltration process for 0.5 hour to finally obtain the silver/copper/nickel/graphene composite material.
Example 8
Firstly, preparing nickel/graphene composite powder
1) Preparing 0.1mol/L nickel nitrate solution and 0.2mol/L glucose solution;
2) mixing a glucose solution with a graphene oxide solution with the concentration of 0.5% according to the mass ratio of 100:1, carrying out ionic stirring to obtain a mixed solution, adding a nickel nitrate solution into the mixed solution according to the volume ratio of 4:5, and continuing the ionic stirring. And (3) carrying out reduction reaction on the nickel nitrate and glucose to generate nickel particles, and adsorbing the graphene oxide by the nickel powder to obtain a nickel/graphene oxide turbid liquid. And (3) centrifugally washing the silver/graphene oxide turbid liquid, and freeze-drying to obtain the nickel/graphene oxide composite powder.
3) And heating and reducing the nickel/graphene oxide composite powder for 3 hours at 620 ℃ in a hydrogen atmosphere to obtain the nickel/graphene oxide composite powder.
Secondly, preparing copper/nickel/graphene composite powder
Copper powder with the particle size of less than 10 microns and nickel/graphene composite powder are mixed according to the mass ratio of 10: 1, uniformly mixing to obtain primary mixed copper/nickel/graphene composite powder, adding the primary mixed copper/nickel/graphene composite powder into a ball mill, and carrying out ball milling for 5 hours at the rotating speed of 250r/min under the protection of argon gas to obtain the copper/nickel/graphene composite powder.
Thirdly, preparing the copper/nickel/graphene composite foam
1) Firstly, heating starch with distilled water until the starch is dissolved to prepare starch water solution with the mass percent of 6%; then adding 5 parts by mass of copper/nickel/graphene composite powder into 1 part by mass of the cooled starch aqueous solution, and uniformly stirring to prepare paste; then the aperture is 0.72mm, and the density is 0.025g/cm 3 The polyurethane sponge is put into pasty/graphene composite powder slurry to be repeatedly soaked until the pores of the polyurethane sponge are filled with the slurry;
2) vacuum drying to remove water in the polyurethane sponge filled with the copper/nickel/graphene composite powder slurry, wherein the vacuum degree is kept at 1Pa, the drying temperature is 80 ℃, and the drying time is 8 hours;
3) putting the polyurethane sponge after vacuum drying into a degreasing furnace for degreasing treatment under the protection of argon, wherein the condition control process comprises the following steps: introducing argon for at least 0.5 hour before heating to remove air in the furnace, raising the temperature from room to 300 ℃ at the speed of 3 ℃/min, and keeping the temperature for 0.5 hour, wherein the argon introduction speed is 0.5L/min; raising the temperature to 400-500 ℃ at the speed of 0.5-1 ℃/min, preserving the temperature for 2-2.5 hours, and introducing argon at the speed of 1L/min; then, turning off a power supply, cooling the degreased intermediate along with the furnace, introducing argon at a rate of 1L/min, and turning off the argon until the intermediate is cooled to room temperature to obtain a degreased copper/nickel/graphene foam intermediate;
4) placing the degreased copper/nickel/graphene foam intermediate in a high-vacuum high-temperature sintering furnace, heating to 800 ℃ at a certain heating rate, and performing vacuum sintering, wherein the vacuum degree of the sintering furnace at least reaches 1 x 10 before heating -3 Pa, from room temperature to 420 ℃ at a rate of 13 ℃/min, maintaining the temperature for 0.8 hour with a vacuum degree of 1X 10 -3 Pa; raising the temperature to 600 ℃ at the speed of 8 ℃/min, and keeping the temperature for 1 hour with the vacuum degree of 1 multiplied by 10 -3 Pa; raising the temperature to 800 ℃ at the speed of 8 ℃/min, and keeping the temperature for 2.5 hours with the vacuum degree of 1 multiplied by 10 -3 Pa; after sintering, the vacuum degree is 1X 10 -3 Pa; cooling to 600 ℃ at the speed of 15 ℃/min, and preserving heat for 1 hour; cooling to 380 deg.C at a rate of 20 deg.C/min, maintaining for 1 hr, and furnace cooling; obtaining a copper/nickel/graphene foam intermediate after vacuum sintering;
5) placing the copper/nickel/graphene foam intermediate after vacuum sintering and cooling in a vacuum annealing furnace, heating to 400 ℃ at a certain heating rate, and performing stress relief annealing treatment, wherein the vacuum degree in the annealing furnace at least reaches 1 x 10 before heating -3 Pa, from room temperature to 400 ℃ at a rate of 15 ℃/min, maintaining the temperature for 4.5 hours at a vacuum of 1X 10 -4 Pa; cooling to 300 deg.C at a rate of 8 deg.C/min, maintaining for 3.5 hr at a vacuum degree of 1 × 10 -4 Pa; cooling to 150 deg.C at a rate of 12 deg.C/min, maintaining for 2 hr at a vacuum degree of 1 × 10 -4 Pa; cooling to room temperature at a rate of 20-23 deg.C/min with a vacuum degree of 1 × 10 - 4 Pa. And finally, carrying out conventional post-treatment to obtain the copper/nickel/graphene foam.
Fourth, infiltration preparation of silver/copper/nickel/graphene composite material
Putting the silver infiltration sheet and the copper/nickel/graphene foam into a mould, putting the mould into an infiltration furnace, and preserving heat at 920 ℃ in a vacuum state7 hours, heating to 1000 ℃ after heat preservation, and filling argon into the furnace when the temperature is reached, wherein the air pressure is 0.5 multiplied by 10 6 Pa, and carrying out a gas pressure infiltration process for 0.5 hour to finally obtain the silver/copper/nickel/graphene composite material.
Performance detection
The mechanical properties and the electrical properties of the silver/copper/nickel/graphene composite material prepared by the technical scheme of the invention are shown in the following table 1.
TABLE 1
Tensile strength (MPa) Elongation (%) Specific resistance (mu omega cm)
Example 1 372 27 2.04
Example 2 391 29 2.03
Example 3 397 31 2.06
Example 4 385 27 2.02
Example 5 389 30 2.02
Example 6 377 28 2.01
Example 7 378 27 2.05
Example 8 381 29 2.03
As can be seen from the table 1, the silver/copper/nickel/graphene composite material prepared by the technical scheme of the invention has tensile strength of 372-397 MPa, elongation of 27-31%, resistivity of 2.01-2.06 mu omega-cm, and excellent mechanical property and electrical property.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, it is possible to make various improvements and modifications without departing from the technical principle of the present invention, and those improvements and modifications assumed in the above are also considered to be within the scope of the present invention.

Claims (9)

1. A preparation method of a silver-based graphene electrical contact material is characterized by comprising the following steps: the method comprises the following steps:
firstly, preparing nickel/graphene composite powder;
secondly, mixing the nickel/graphene composite powder prepared in the first step with copper powder to prepare copper/nickel/graphene composite powder;
thirdly, preparing the copper/nickel/graphene composite powder prepared in the second step into a copper/nickel/graphene composite foam;
fourthly, infiltrating the copper/nickel/graphene composite foam body prepared in the third step with a silver infiltration sheet to obtain a silver/copper/nickel/graphene composite electric contact material;
the third step comprises:
adding copper/nickel/graphene composite powder into a starch aqueous solution, and uniformly stirring to prepare paste; then putting the polyurethane sponge into pasty/graphene composite powder slurry for repeated impregnation until the pores of the polyurethane sponge are filled;
vacuum drying is carried out to remove the moisture in the polyurethane sponge filled with the copper/nickel/graphene composite powder slurry;
putting the polyurethane sponge after vacuum drying into a degreasing furnace for degreasing under the protection of protective gas;
placing the degreased copper/nickel/graphene foam intermediate in a high-vacuum high-temperature sintering furnace, and heating to 800-850 ℃ at a certain heating rate for vacuum sintering;
and (3) placing the copper/nickel/graphene foam intermediate after vacuum sintering and cooling in a vacuum annealing furnace for stress relief annealing treatment.
2. The method for preparing the silver-based graphene electrical contact material according to claim 1, wherein the method comprises the following steps: the first step comprises the following steps:
preparing 0.1mol/L nickel nitrate solution and 0.2mol/L glucose solution;
mixing a glucose solution and a graphene oxide solution with the concentration of 0.5% according to the mass ratio of 100:1, carrying out ion stirring to obtain a mixed solution, adding a nickel nitrate solution into the mixed solution according to the volume ratio of 4:5, and continuing to carry out ion stirring; carrying out reduction reaction on nickel nitrate and glucose to generate nickel particles, adsorbing graphene oxide by nickel powder to obtain a nickel/graphene oxide suspension, centrifugally washing the silver/graphene oxide suspension, and freeze-drying to obtain nickel/graphene oxide composite powder;
and heating and reducing the nickel/graphene oxide composite powder for 3-4 hours at 580-620 ℃ in a hydrogen atmosphere to obtain the nickel/graphene oxide composite powder.
3. The method for preparing the silver-based graphene electrical contact material according to claim 1, wherein the method comprises the following steps: the second step comprises the following steps: copper powder with the particle size of less than 10 microns and the nickel/graphene composite powder are mixed according to the mass ratio of 10: 1, uniformly mixing to obtain primary mixed copper/nickel/graphene composite powder, adding the primary mixed copper/nickel/graphene composite powder into a ball mill, and carrying out ball milling for 5-6 hours at a rotation speed of 250r/min under the protection of argon gas to obtain the copper/nickel/graphene composite powder.
4. The method for preparing the silver-based graphene electrical contact material according to claim 1, wherein: the third step comprises: heating starch with distilled water until the starch is dissolved to prepare a starch water solution with the mass percent of 5-8%; then adding 3-5 parts by mass of copper/nickel/graphene composite powder into 1 part by mass of the cooled starch aqueous solution, and uniformly stirring to prepare paste; then, the aperture is 0.56-0.72 mm, the density is 0.025-0.035 g/cm 3 The polyurethane sponge is put into pasty/graphene composite powder slurry to be repeatedly soaked until the pores of the polyurethane sponge are filled with the slurry; and (3) vacuum drying to remove water in the polyurethane sponge filled with the copper/nickel/graphene composite powder slurry, wherein the vacuum degree is kept at 1-3 Pa, the drying temperature is 50-80 ℃, and the drying time is 4-8 hours.
5. The method for preparing the silver-based graphene electrical contact material according to claim 1, wherein: the third step comprises the following steps: putting the polyurethane sponge after vacuum drying into a degreasing furnace for degreasing treatment under the protection of argon, wherein the condition control process comprises the following steps: introducing argon for at least 0.5 hour before heating to remove air in the furnace, raising the temperature from room to 250-300 ℃ at the speed of 1-3 ℃/min, preserving the temperature for 0.5-1 hour, and introducing argon at the speed of 0.5L/min; raising the temperature to 400-500 ℃ at the speed of 0.5-1 ℃/min, preserving the temperature for 2-2.5 hours, and introducing argon at the speed of 1L/min; and then turning off the power supply, cooling the degreased intermediate along with the furnace, introducing argon at the speed of 1L/min, and turning off the argon until the intermediate is cooled to room temperature to obtain the degreased copper/nickel/graphene foam intermediate.
6. The method for preparing the silver-based graphene electrical contact material according to claim 1, wherein the method comprises the following steps: the third step comprises: placing the degreased copper/nickel/graphene foam intermediate into a high-vacuum high-temperature sintering furnace, heating to 800-850 ℃ at a certain heating rate, and performing vacuum sintering, wherein the vacuum degree of the sintering furnace at least reaches 1 x 10 before heating -3 Pa, raising the temperature from room temperature to 380-420 ℃ at the speed of 10-15 ℃/min, and keeping the temperature for 0.5-1 hour, wherein the vacuum degree is 1 multiplied by 10 -4 Pa; raising the temperature to 600-650 ℃ at a rate of 8-10 ℃/min, preserving the heat for 0.5-1 hour, and keeping the vacuum degree at 1 x 10 -4 Pa～1×10 -3 Pa; raising the temperature to 800-850 ℃ at the speed of 6-8 ℃/min, preserving the heat for 2-2.5 hours, and keeping the vacuum degree at 1 multiplied by 10 -4 Pa～1×10 -3 Pa; after sintering, the vacuum degree is 1X 10 -4 Pa～1×10 -3 Pa; cooling to 600-650 ℃ at the speed of 12-15 ℃/min, and preserving heat for 1-1.5 hours; cooling to 380-420 ℃ at the speed of 15-20 ℃/min, preserving heat for 1-1.5 hours, and then cooling along with the furnace; and obtaining the copper/nickel/graphene foam intermediate after vacuum sintering.
7. The method for preparing the silver-based graphene electrical contact material according to claim 1, wherein the method comprises the following steps: the third step comprises: placing the copper/nickel/graphene foam intermediate after vacuum sintering and cooling in a vacuum annealing furnace, heating to 350-400 ℃ at a certain heating rate, and performing stress relief annealing treatment, wherein the vacuum degree in the annealing furnace at least reaches 1 x 10 before heating - 3 Pa, raising the temperature from room temperature to 350-400 ℃ at the speed of 12-15 ℃/min, and keeping the temperature for 4-4.5 hours with the vacuum degree of 1 multiplied by 10 -4 Pa～1×10 -3 Pa; cooling to 300-330 ℃ at the speed of 5-8 ℃/min, preserving the heat for 3-3.5 hours,vacuum degree of 1X 10 -4 Pa～1×10 -3 Pa; cooling to 150-200 ℃ at the speed of 10-12 ℃/min, preserving the heat for 1.5-2 hours, and keeping the vacuum degree at 1 multiplied by 10 -4 Pa～1×10 -3 Pa; cooling to room temperature at a rate of 20-23 deg.C/min with a vacuum degree of 1 × 10 -4 Pa; copper/nickel/graphene foam was prepared.
8. The method for preparing the silver-based graphene electrical contact material according to claim 1, wherein the method comprises the following steps: the fourth step comprises: putting a silver infiltration sheet and a copper/nickel/graphene foam into a mold, putting the mold into an infiltration furnace, preserving heat for 7-8 hours at 900-930 ℃ in a vacuum state, heating to 980-1000 ℃ after heat preservation, filling argon into the furnace at the temperature, wherein the air pressure is 0.5-1 multiplied by 10 6 Pa, and carrying out air pressure infiltration for 0.5-1 hour to finally obtain the silver/copper/nickel/graphene composite material.
9. A silver-based graphene electrical contact material prepared according to the method of any one of claims 1 to 8.
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